The laser driven hydrogen atom.

Ciaran McCormick
Queens University Belfast
March 28th, 2012
Ciaran McCormick (Queens University Belfast) March 28th, 2012 1 / 16
Recap 1
The Time Dependent Schodinger Equation
i

t
= H
The Time Dependent Hamiltonian
H =
1
2

1
r

i
c
A
z
(t)

z
Wavefunction
(r, t) =

=0
f

(r , t)
r
Y
,m
(, )
Ciaran McCormick (Queens University Belfast) March 28th, 2012 2 / 16
Recap 2
TDSE
i

t

=0
1
r
f

(r , t)Y
,0
(, ) = H

=0
1
r
f

(r , t)Y
,0
(, )
Orthogonality and Spherical Harmonics
_
2
0
d
_

0
d sin Y

,m
(, )Y

,m
(, ) =
,

m,m

TDSE depending only on radial distance and time

i

t
f

(r , t)
r
=

=0
_
Y

,0
(, )H
f

(r , t)
r
Y
,0
(, ) d
Ciaran McCormick (Queens University Belfast) March 28th, 2012 3 / 16
Recap 3
Laplacian Operator

2
=
1
r
2

r
_
r
2

r
_
+
1
r
2
_
1
sin

_
sin

_
+
1
sin
2

2
_
Spherical Harmonic Eigenvalue Equation

_
1
sin

_
sin

_
+
1
sin
2

2
_
Y
,0
(, ) = ( + 1)Y
,0
(, )
TDSE
i
r

t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

i
c
A
z
(t)

_
Y

,0
(, )

z
_
Y
,0
(, )
f

r
_
d
Ciaran McCormick (Queens University Belfast) March 28th, 2012 4 / 16
Recap 3
Laplacian Operator

2
=
1
r
2

r
_
r
2

r
_
+
1
r
2
_
1
sin

_
sin

_
+
1
sin
2

2
_
Spherical Harmonic Eigenvalue Equation

_
1
sin

_
sin

_
+
1
sin
2

2
_
Y
,0
(, ) = ( + 1)Y
,0
(, )
TDSE
i
r

t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

i
c
A
z
(t)

_
Y

,0
(, )

z
_
Y
,0
(, )
f

r
_
d
Ciaran McCormick (Queens University Belfast) March 28th, 2012 4 / 16
Recap 3
Laplacian Operator

2
=
1
r
2

r
_
r
2

r
_
+
1
r
2
_
1
sin

_
sin

_
+
1
sin
2

2
_
Spherical Harmonic Eigenvalue Equation

_
1
sin

_
sin

_
+
1
sin
2

2
_
Y
,0
(, ) = ( + 1)Y
,0
(, )
TDSE
i
r

t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

r
Ciaran McCormick (Queens University Belfast) March 28th, 2012 4 / 16
Recap 4: TDSE
TDSE - No laser eld
i

t
f

(r , t) =
_

1
2
d
2
dr
2
+
( + 1)
2r
2

1
r
_
f

(r , t)
Separation of Variables
f

(r , t) = g

(r )T

(t)
Radial Dependent Part
_

1
2
d
2
dr
2
+
( + 1)
r
2

1
r
_
g

(r ) = E g

(r )
Time Dependent Part
dT
dt
= iET(t)
T = e
iEt
Ciaran McCormick (Queens University Belfast) March 28th, 2012 5 / 16
Recap 5: Time Independent Schodinger Equation
Eigenvalue Problem
Finite Dierence Equation
d
2
dr
2
(f

(r , t)) =
f

(r + r , t) 2f

(r , t) + f

(r r , t)
(r )
2
where the red blocks are,

1
2(r )
2
and the black blocks are given by
( + 1)
r
2

1
r
+
1
(r )
2
Ciaran McCormick (Queens University Belfast) March 28th, 2012 6 / 16
Some Results
N = 999, b = 50.0au and E is in atomic units
l

E
estimate
E
actual
0 -0.499687890015716 -0.5
1 -0.125006512903812 -0.125
2 -5.555581160715379E-002 -5.555555596947670E-002
3 -3.124571705439556E-002 -3.125000000000000E-002
4 -1.977527744935510E-002 -1.999999955296516E-002
5 -1.242637199326190E-002 -1.388888899236917E-002
6 -6.147446767590584E-003 -1.020408142358065E-002
7 -1.577378457009712E-005 -7.812500000000000E-003
8 6.274400917348134E-003 -6.172839552164078E-003
9 1.284838845282180E-002 -4.999999888241291E-003
10 1.976679202690924E-002 -4.132231231778860E-003
Ciaran McCormick (Queens University Belfast) March 28th, 2012 7 / 16
Time Dependent Schr odinger Equation
TDSE
i

t
(r, t) = H(r, t)
TDSE
i
r

t
f

=
( + 1)
2r
2
f

r

1
2
f

r

1
r
f

i
c
A
z
(t)

=0
_
Y

,0
(, )

z
_
Y
,0
(, )
f

r
_
d
Ciaran McCormick (Queens University Belfast) March 28th, 2012 8 / 16
Time Dependent Schr odinger Equation
Partial Derivative

z
= cos

r

sin
r

Inserting the partial derivative

i
c
A
z
(t)

=0
__
Y

,0
sin
d
d
(Y
,0
(, )) d
_
f

(r , t)
r
2

i
c
A
z
(t)

=0
__
Y

,0
(, ) cos Y
,0
(, ) d
_

r
_
f

(r , t)
r
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 9 / 16
Final TDSE
i

t
f

(r , t) =
_

1
2
d
2
dr
2
+
( + 1)
2r
2

1
r
_
f

(r , t)
+
i
c
A
z
(t)
_

_
(2 + 1)(2 1)
_

r


r
_
f
1
(r , t)

( + 1)
_
(2 + 1)(2 + 3)
_
( + 1)
r
+

r
_
f
+1
(r , t)
_
Finite Dierence Equation, First Derivative
d
dr
(f

(r , t)) =
f

(r + r , t) f

(r r , t)
2r
Finite Dierence Equation, Second Derivative
d
2
dr
2
(f

(r , t)) =
f

(r + r , t) f

(r , t) + f

(r r , t)
(r )
2
Ciaran McCormick (Queens University Belfast) March 28th, 2012 10 / 16
Diagrammatic Representation
Algebraic Eigenvalue Problem
Black Diagonal
( + 1)
2r
2

1
r
+
1
(r )
2
Blue Diagonals

1
2
_
1
(r )
2
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 11 / 16
Diagrammatic Representation
Eigenvalue-Eigenvector Problem
+ 1,r Red Supra-Diagonal

i
c
A
z
(t)
_
( + 1)
2
r
_
(2 + 1)(2 + 3)
_
1,r Red Sub-Diagonal
i
c
A
z
(t)
_

2
r
_
(2 + 1)(2 1)
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 12 / 16
Diagrammatic Representation
Algebraic Eigenvalue Problem
+ 1, r+1 Green Supra-Diagonal

i
c
A
z
(t)
_
( + 1)
2r
_
(2 + 1)(2 + 3)
_
1, r-1 Green Sub-Block
i
c
A
z
(t)
_

2r
_
(2 + 1)(2 1)
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 13 / 16
Diagrammatic Representation
Algebraic Eigenvalue Problem
1, r+1 Purple Supra-Block

i
c
A
z
(t)
_

2r
_
(2 + 1)(2 1)
_
+ 1, r-1 Purple Sub-Diagonal
i
c
A
z
(t)
_
( + 1)
2r
_
(2 + 1)(2 + 3)
_
Ciaran McCormick (Queens University Belfast) March 28th, 2012 14 / 16
Time Propagation
TDSE
i

= H
Taylor Series Expansion
(t + t) = (t) + t

(t) +
(t)
2
2!

(t) + . . .
From the TDSE we can see that

(t) =
H(t)(t)
i
Dierentiating with respect to t

(t) =

H(t)(t) + H(t)

(t)
i

H(t)

(t)
i
Ciaran McCormick (Queens University Belfast) March 28th, 2012 15 / 16
Time Propagation 2
Substituting in the expression for the rst derivative

(t)
H
2
(t)(t)
i
The third derivative can be found similarly
...

(t)
H
3
(t)(t)
i
3
Time Propagator
(t+t) (t)+
tH(t)(t)
i
+
(t)
2
H
2
(t)(t)
i
2
2!
+ +
(t)
n
H
n
(t)(t)
i
n
n!
Ciaran McCormick (Queens University Belfast) March 28th, 2012 16 / 16